This work is devoted to the study of thermometric performances of Nd3+ (0.1 or 0.5 mol.%), Yb3+ (X%):YF3 nanoparticles. Temperature sensitivity of spectral shape is related to the phonon-assisted nature of energy transfer (PAET) between Nd3+ and Yb3+). However, in the case of single-doped Nd3+ (0.1 or 0.5 mol.%):YF3 nanoparticles, luminescence decay time (LDT) of 4F3/2 level of Nd3+ in Nd3+ (0.5 mol.%):YF3 decreases with the temperature decrease. In turn, luminescence decay time in Nd3+ (0.1 mol.%):YF3 sample remains constant. It was proposed, that at 0.5 mol.% the cross-relaxation (CR) between Nd3+ ions takes place in contradistinction from 0.1 mol.% Nd3+ concentration. The decrease of LDT with temperature is explained by the decrease of distances between Nd3+ with temperature that leads to the increase of cross-relaxation efficiency. It was suggested, that the presence of both CR and PAET processes in the studied system (Nd3+ (0.5 mol.%), Yb3+ (X%):YF3) nanoparticles provides higher temperature sensitivity compared to the systems having one process (Nd3+ (0.1 mol.%), Yb3+ (X%):YF3). The experimental results confirmed this suggestion. The maximum relative temperature sensitivity was 0.9%·K−1 at 80 K.